EP0909802A1 - Hydrofuge oleofuge fluore en dispersion aqueuse - Google Patents

Hydrofuge oleofuge fluore en dispersion aqueuse Download PDF

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Publication number
EP0909802A1
EP0909802A1 EP97924312A EP97924312A EP0909802A1 EP 0909802 A1 EP0909802 A1 EP 0909802A1 EP 97924312 A EP97924312 A EP 97924312A EP 97924312 A EP97924312 A EP 97924312A EP 0909802 A1 EP0909802 A1 EP 0909802A1
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EP
European Patent Office
Prior art keywords
fluorine
oil
group
aqueous dispersion
repellent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97924312A
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German (de)
English (en)
Other versions
EP0909802A4 (fr
Inventor
Masayuki Yodogawa Works YAMANA
Norimasa Yodogawa Works UESUGI
Eiji Yodogawa Works OGURA
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Daikin Industries Ltd
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Daikin Industries Ltd
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Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP0909802A1 publication Critical patent/EP0909802A1/fr
Publication of EP0909802A4 publication Critical patent/EP0909802A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to an aqueous dispersion-type fluorine-containing water- and oil-repellent having excellent fastness to rubbing.
  • aqueous dispersion-type fluorine-containing water- and oil-repellents prepared by emulsion-polymerisation of a perfluoroalkyl group-containing methacrylate or acrylate ester with a monomer copolymerizable therewith have been used to confer water- and oil-repellency on a textile.
  • these water- and oil-repellents are produced by emulsion-polymerization in the presence of a hydrocarbon-based emulsifier.
  • a dyed fabric made of fibers is subjected to water- and oil-repellency treatment with a fluorine-containing compound, there is the disadvantage of reduction of dye fastness to rubbing.
  • a composition comprising a fluorine-containing compound and a specific polysiloxane has been proposed (Japanese Patent Kokoku Publication No. 1232/1983). Further, a composition comprising a glycol and a fluorine-containing compound has also been proposed (Japanese Patent Kokai Publication No. 173772/1995).
  • these compositions are not adequate in respect of fastness to rubbing.
  • fabrics composed of micro-fibers referred to collectively as new synthetic fibers have not achieved satisfactory results under the present circumstances.
  • An object of the present invention is to provide an aqueous dispersion-type fluorine-containing water- and oil-repellent excellent in fastness to rubbing.
  • the present invention provides an aqueous dispersion-type fluorine-containing water- and oil-repellent wherein (A) a fluorine-containing copolymer comprising (A-1) a monomer having a polyfluoroalkyl group and (A-2) a monomer copolymerizable therewith is dispersed in the presence of (B) an emulsifier comprising a fluorine-containing cationic surfactant.
  • Examples of the polyfluoroalkyl group-containing monomer (A-1) in the present invention include the following polyfluoroalkyl group-containing (meth)acrylates: wherein R f is a C 3 -C 21 polyfluoroalkyl group or polyfloroalkenyl group, R 1 is hydrogen or a C 1 -C 10 alkyl group, R 2 is a C 1 -C 10 alkylene group, R 3 is hydrogen or a methyl group, Ar is an arylene group which may have a substituent group, and n is an integer of 1 to 10.
  • the polyfluoroalkyl group-containing monomer (A-1) may be used as a mixture of at least two.
  • the other monomer (A-2) copolymerizable with the polyfluoroalkyl group-containing monomer (A-1) includes, but is not limited to, known compounds having a polymerizable unsaturated linkage.
  • the monomer (A-2) may be a monomer containing no fluorine atom.
  • the other monomer (A-2) copolymerized include (meth)acrylates such as 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyalkyl (meth)acrylate, polyoxyalkylene (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.
  • (meth)acrylates such as 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, hydroxyalkyl (meth)acrylate, polyoxyalkylene (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, gly
  • the other monomer (A-2) can be used alone or in combination of at least two of the above compounds.
  • a weight ratio of the polyfluoroalkyl group-containing monomer (A-1) to the other monomer (A-2) may be from 30 : 70 to 90 : 10, more preferably from 50 : 50 to 80 : 20.
  • a molecular weight of the copolymer may be from 500 to 1,000,000.
  • the fluorine-containing cationic surfactant in the emulsifier (B) has lower affinity for dyestuffs than usual hydrocarbon-based surfactants, and the dyed fabric treated with the water- and oil-repellent comprising the fluorine-containing cationic surfactant does not cause dyestuffs to be raised on the surface and is thus excellent in fastness to rubbing.
  • the fluorine-containing cationic surfactant includes, but is not limited to, a compound of the following formula:
  • R 11 and R 12 are CH 3 -, C 2 H 5 -, C 4 H 9 - and -CH 2 -CH 2 -OH.
  • R 13 are CH 3 -, C 2 H 5 - and Ph-CH 2 - (Ph is a phenyl group).
  • X are Cl, Br and I.
  • fluorine-containing cationic surfactant examples include:
  • a process for producing the copolymer (A) in the aqueous dispersion-type fluorine water-repellent and oil-repellent of the present invention is preferably an emulsion polymerisation.
  • a conventional method can be used for the emulsion polymerization.
  • the monomers (A-1) and (A-2) are emulsified in an aqueous medium in the presence of an emulsifier and polymerised by adding a polymerization initiator to the emulsion.
  • the emulsifier (B) may consist of the fluorine-containing cationic surfactant but may contain other emulsifier (e.g. a fluorine-free surfactant, a fluorine-containing nonionic surfactant and a fluorine-containing anionic surfactant) than the fluorine-containing cationic surfactant.
  • a fluorine-free surfactant e.g. a fluorine-free surfactant, a fluorine-containing nonionic surfactant and a fluorine-containing anionic surfactant
  • the amount of the fluorine-containing cationic surfactant is at least 15 parts, preferably at least 30 parts by weight, based on 100 parts by weight of the emulsifier (B).
  • the amount of the emulsifier (B) is from 0.5 to 15 parts by weight based on 100 parts by weight of the whole monomers.
  • a conventional chain transfer agent such as mercaptan can be used for the polymerization.
  • the process for producing the copolymer comprising the monomer (A-1) having a polyfluoroalkyl group and the monomer (A-2) copolymerizable therewith in the aqueous dispersion-type fluorine-containing water- and oil-repellent of the present invention is not particularly limited, but in consideration of convenience described above, the copolymer is preferably prepared by the above-described emulsification polymerization.
  • the polymer may be synthesized by a conventional solution polymerization, suspension polymerization or the like, and afier isolation of the polymer, it can be formed into an aqueous dispersion by use of the emulsifier containing the fluorine-containing cationic surfactant as the essential component.
  • another water- and oil-repellent agent, a softening agent, an antistatic agent, a cross-linking agent and an anticrease agent may be contained in the aqueous dispersion-type water- and oil-repellent of the present invention.
  • a substrate treated with the aqueous dispersion-type water- and oil-repellent of the present invention is not limited insofar as it is a textile, and a wide variety of examples can be mentioned.
  • animal and vegetable-originated natural fibers such as cotton, hemp, wool and silk
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene
  • semi-synthetic fibers such as rayon and acetate; as well as fiber blends thereof
  • the aqueous dispersion-type water- and oil-repellent of the present invention can adhere to the surface of the substrate to be treated by e.g. conventional immersion coating, and then be dried. If necessary, the repellent may be applied together with a suitable cross-linking agent so that the repellent is cured.
  • Water repellency is expressed in terms of water repellency No. (see Table 1 below) by a spray method in accordance with JIS (Japanese Industrial Standard) L-1092.
  • oil repellency a few drops of a test solution shown in Table 2 were dropped on two positions on a test cloth, and 30 seconds later, the penetration state was observed to evaluate oil repellency according to AATCC-TM118. Fastness to rubbing was evaluated in a gray scale for pollution (6 levels from Grade 0 to Grade 5) (see Table 3) in a vibration crockmeter using a white cotton cloth as abrasion cloth after the cloth was rubbed back and forth 200 times at a load of 500 g. Water repellency No.
  • fluorine-containing cationic surfactant A 5 g
  • polyoxyethylene nonyl phenyl ether 5 g
  • DPM dipropylene glycol monomethyl ether
  • the mixture was emulsified with a high-pressure homogenizer at a temperature of 60°C under a pressure of 400 kg/cm 2 to give a milky-white emulsion.
  • 15 g of vinyl chloride (VC) from a bomb was added thereto, and the atmosphere was replaced by nitrogen for about 60 minutes.
  • polymerization was initiated by addition of 2,2'-azobis(2-methylpropionamidine)dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 g).
  • V-50 2,2'-azobis(2-methylpropionamidine)dihydrochloride
  • the reaction mixture was cooled at 40°C or less to give an emulsion having a solid content of about 33 %.
  • the degree of conversion (that is, degree of polymerization) of FA determined by gas chromatography was 99.7 %, and the degree of conversion (that is, degree of polymerization) of the whole monomers was 95 %.
  • the mixture was emulsified with a high-pressure homogenizer at a temperature of 60°C under a pressure of 400 kg/cm 2 to give a milky-white emulsion.
  • a high-pressure homogenizer at a temperature of 60°C under a pressure of 400 kg/cm 2 to give a milky-white emulsion.
  • polymerization was initiated by addition of 2,2'-azobis(2-methylpropion-amidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 g).
  • V-50 2,2'-azobis(2-methylpropion-amidine) dihydrochloride
  • the reaction mixture was cooled at 40°C or less to give an emulsion having a solid content of about 33 %.
  • the degree of conversion of FA determined by gas chromatography was 99 %, and the degree of conversion of the whole monomers was 97 %.
  • Emulsion polymerisation was conducted in the same manner as in Example 1 or 2 using a charge composition shown in Table I, and as a result, an emulsion having a solid content of 33 % was obtained.
  • the degrees of conversion of FA and the whole monomers as determined by gas chromatography are shown in Table I.
  • Emulsion polymerization was conducted in the same manner as in Example 1 or 2 using a charge composition shown in Table I, and as a result, an emulsion having a solid content of about 33 % was obtained.
  • the degrees of conversion of FA and the whole monomers as determined by gas chromatography are shown in Table I.
  • each of the emulsions obtained in the Examples and Comparative Examples was adjusted to 20 % with water and further adjusted to 1 % with water to give a treatment liquid.
  • a polyester macro-fiber fabric was immersed in this treatment liquid, and then squeezed with a mangle such that the wet pickup of the fabric was about 65 %.
  • the treated fabric was dried at 100°C for 2 minutes and further heat-treated at 130°C for 3 minutes.
  • the resulting test fabric was evaluated for water repellency, oil repellency, and fastness to rubbing. The results are shown in Table II.
  • Example 1 Water repellency Oil repellency Fastness to rubbing Example 1 100 6 4 - 5 Example 2 100 6 5 Example 3 100 7 4 Example 4 100 7 4 Example 5 100 6 4 - 5 Example 6 100 6 5 Example 7 100 6 4 Comparative Example 1 100 5 2 Comparative Example 2 100 6 2 Comparative Example 3 100 5 2

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
EP97924312A 1996-06-21 1997-06-04 Hydrofuge oleofuge fluore en dispersion aqueuse Withdrawn EP0909802A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP161942/96 1996-06-21
JP8161942A JPH108041A (ja) 1996-06-21 1996-06-21 水分散型フッ素系撥水撥油剤
PCT/JP1997/001894 WO1997048780A1 (fr) 1996-06-21 1997-06-04 Hydrofuge oleofuge fluore en dispersion aqueuse

Publications (2)

Publication Number Publication Date
EP0909802A1 true EP0909802A1 (fr) 1999-04-21
EP0909802A4 EP0909802A4 (fr) 2000-03-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97924312A Withdrawn EP0909802A4 (fr) 1996-06-21 1997-06-04 Hydrofuge oleofuge fluore en dispersion aqueuse

Country Status (6)

Country Link
US (1) US6126849A (fr)
EP (1) EP0909802A4 (fr)
JP (1) JPH108041A (fr)
KR (1) KR20000016701A (fr)
TW (1) TW474985B (fr)
WO (1) WO1997048780A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032800A1 (fr) * 1999-10-29 2001-05-10 Asahi Glass Company, Limited Dispersion aqueuse pour repulsif eau et huile et procede de production
WO2002006433A1 (fr) * 2000-07-17 2002-01-24 Unilever Plc Composition de lessive comprenant un polymere antisalissure a base de perfluoroalkyle
EP1338637A1 (fr) * 2000-09-21 2003-08-27 Daikin Industries, Ltd. Dispersion aqueuse d'eau et de d'oleofuge de son procede de fabrication
WO2004033579A1 (fr) * 2002-10-10 2004-04-22 Seimi Chemical Co., Ltd. Composition de barriere anti-huile
EP1533356A1 (fr) * 2003-11-24 2005-05-25 3M Innovative Properties Company Composition fluorochimique pour rendre des substrats oléophobes et/ou hydrophobes
US7015275B1 (en) 1999-04-07 2006-03-21 Daikin Industries, Ltd. Aqueous water-and oil-repellent dispersion
CN102352000A (zh) * 2011-07-14 2012-02-15 浙江大学 有机-无机复合疏水/疏油表面处理剂的合成方法

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3138423A1 (de) * 1981-09-26 1983-04-14 Basf Ag, 6700 Ludwigshafen Trennung von stoffmischungen
JP4457497B2 (ja) * 1998-12-22 2010-04-28 ダイキン工業株式会社 撥水撥油剤水性分散液
JP2000212549A (ja) 1999-01-25 2000-08-02 Asahi Glass Co Ltd 撥水撥油剤組成物およびその製造方法
US6174964B1 (en) * 1999-09-24 2001-01-16 3M Innovative Properties Company Fluorochemical oligomer and use thereof
WO2002064696A1 (fr) * 2001-01-30 2002-08-22 Daikin Industries, Ltd. Composition hydrofuge et oléofuge, procédé de fabrication et utilisation
WO2002102758A1 (fr) * 2001-06-18 2002-12-27 Honeywell International, Inc. Composes renfermant du fluor et polymeres tires de ces composes
US7279522B2 (en) 2001-09-05 2007-10-09 3M Innovative Properties Company Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant
EP1329548A1 (fr) * 2002-01-21 2003-07-23 3M Innovative Properties Company Procédé pour le traitement hydrofuge et oléofuge d'un tissu ou non-tissé
DE60214343T2 (de) * 2002-05-22 2007-03-29 3M Innovative Properties Co., Saint Paul Prozess zur Reduzierung des Gehaltes an fluorierten Emulgatoren in wässrigen Fluorpolymer-Dispersionen
KR20030097201A (ko) * 2002-06-20 2003-12-31 니카코리아 (주) 수분산 불소계 발수발유제 및 그 제조방법
EP1441014A1 (fr) * 2003-01-22 2004-07-28 3M Innovative Properties Company Dispersion aqueuse d'un polymère fluoré comprenant un polymère fluoré thermoprocessable avec un contenu réduit de surfactants fluorés
ATE302243T1 (de) * 2003-02-28 2005-09-15 3M Innovative Properties Co Fluoropolymerdispersion enthaltend kein oder wenig fluorhaltiges netzmittel mit niedrigem molekulargewicht
EP1493761A1 (fr) * 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymère basé sur les acrylates ou les méthacrylates avec des courtes chaínes fluorées, et leurs compositions du type imperméable à l'eau et à l'huile
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CN100463931C (zh) * 2003-11-03 2009-02-25 长春赛纳纳米服饰有限公司 一种纳米材料改性的织物整理剂及其制备方法
EP1533325B1 (fr) * 2003-11-17 2011-10-19 3M Innovative Properties Company Dispersions aqueuses de polytétrafluoroéthylène avec un contenu réduit de surfactants fluorés
EP1561742B1 (fr) * 2004-02-05 2012-11-21 3M Innovative Properties Company Procédé de récupération de tensioactifs acide fluorés à partir des adsorbants chargés en ces tensioactifs
EP1561729A1 (fr) * 2004-02-05 2005-08-10 3M Innovative Properties Company Elimination de tensioactifs fluorés présents dans les eaux usées
US7723417B2 (en) * 2004-03-25 2010-05-25 3M Innovative Properties Company Fluorochemical composition and method for treating a substrate therewith
EP1614731B1 (fr) 2004-07-05 2008-08-27 3M Innovative Properties Company Revêtement primaire à base de PTFE pour substrat métallique
US8440779B2 (en) 2004-11-04 2013-05-14 3M Innovative Properties Company Carbodiimide compound and compositions for rendering substrates oil and water repellent
EP1700869A1 (fr) * 2005-03-11 2006-09-13 3M Innovative Properties Company Récupération de tensioactifs fluorés d'une résine basique anionique contenant des groupes ammonium quaternaire
GB0523853D0 (en) 2005-11-24 2006-01-04 3M Innovative Properties Co Fluorinated surfactants for use in making a fluoropolymer
US20070015937A1 (en) 2005-07-15 2007-01-18 3M Innovative Properties Company Process for recovery of fluorinated carboxylic acid surfactants from exhaust gas
GB0514398D0 (en) 2005-07-15 2005-08-17 3M Innovative Properties Co Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
GB0525978D0 (en) 2005-12-21 2006-02-01 3M Innovative Properties Co Fluorinated Surfactants For Making Fluoropolymers
US20080015304A1 (en) 2006-07-13 2008-01-17 Klaus Hintzer Aqueous emulsion polymerization process for producing fluoropolymers
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
CN100383336C (zh) * 2006-04-25 2008-04-23 辽宁氟材料研究院有限公司 一种乳液型含氟织物整理剂及其制法
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US8119750B2 (en) 2006-07-13 2012-02-21 3M Innovative Properties Company Explosion taming surfactants for the production of perfluoropolymers
GB0625071D0 (en) * 2006-12-15 2007-01-24 3M Innovative Properties Co Process for removing fluorinated emulsifier from fluoropolmer dispersions using an ion-exchange resin and dispersions obtained therefrom
US7964657B2 (en) * 2007-03-23 2011-06-21 Peach State Labs, Inc. Polymeric dispersions and applications thereof
JP5453250B2 (ja) 2007-06-06 2014-03-26 スリーエム イノベイティブ プロパティズ カンパニー フッ素化エーテル組成物及びフッ素化エーテル組成物の使用方法
US8178004B2 (en) * 2008-06-27 2012-05-15 Aculon, Inc. Compositions for providing hydrophobic layers to metallic substrates
CN102317403A (zh) 2008-12-18 2012-01-11 3M创新有限公司 使含烃地层与氟化醚组合物接触的方法
CN102333825B (zh) 2008-12-31 2014-02-26 埃西勒国际通用光学公司 增强导电性聚合物基涂料的抗静电性能的添加剂
EP2248865A1 (fr) 2009-05-07 2010-11-10 Essilor International (Compagnie Générale D'Optique) Compositions de gel/sol antistatiques et articles optiques revêtus avec celles-ci
EP2450193B1 (fr) 2010-11-09 2015-05-06 ESSILOR INTERNATIONAL (Compagnie Générale d'Optique) Procédé de coloration d'articles et compositions pouvant être colorées à utiliser dans ce procédé
EP2829572B1 (fr) * 2012-03-23 2019-04-24 Daikin Industries, Ltd. Composition d'émulsion aqueuse
US11148361B2 (en) 2016-01-21 2021-10-19 3M Innovative Properties Company Additive processing of fluoroelastomers
EP3655471A2 (fr) 2017-07-19 2020-05-27 3M Innovative Properties Company Procédé de fabrication d'articles polymères et de composites polymères par fabrication additive et articles polymères et composites
CA3070323A1 (fr) 2017-07-19 2019-01-24 3M Innovative Properties Company Traitement additif de fluoropolymeres
KR102281760B1 (ko) 2018-07-12 2021-07-23 주식회사 엘지화학 다공성 불소계 수지 복합막 및 이의 제조 방법

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5571779A (en) * 1978-11-22 1980-05-30 Daikin Ind Ltd Water- and oil-repellent aqueous dispersion composition
JPS581232B2 (ja) * 1980-02-29 1983-01-10 大日本インキ化学工業株式会社 染色摩擦堅牢度の改良された繊維布の撥水撥油加工法
JPS58126372A (ja) * 1982-01-23 1983-07-27 第一工業製薬株式会社 繊維製品仕上処理用組成物およびそれを用いる繊維製品の撥水撥油仕上処理方法
JPS61264081A (ja) * 1985-05-18 1986-11-21 Daikin Ind Ltd 撥水撥油剤分散液
FR2588555B1 (fr) * 1985-10-16 1987-12-11 Atochem Monomeres acryliques fluores, polymeres en derivant et leur application au traitement hydrofuge et oleofuge de substrats divers
FR2590895B1 (fr) * 1985-12-03 1988-01-15 Atochem Monomeres acryliques fluores, polymeres en derivant et leur application comme agents hydrophobes et oleophobes
JPS6314027A (ja) * 1986-06-30 1988-01-21 Matsushita Seiko Co Ltd 熱交換換気装置
JP2817212B2 (ja) * 1989-06-22 1998-10-30 ダイキン工業株式会社 撥水撥油剤組成物
DE3935859A1 (de) * 1989-10-27 1991-05-02 Bayer Ag Dispersionen von perfluoralkylgruppen enthaltende copolymerisate
JP2508343B2 (ja) * 1990-02-21 1996-06-19 旭硝子株式会社 フッ素系撥水撥油剤組成物
JP3064388B2 (ja) * 1990-10-29 2000-07-12 大日本インキ化学工業株式会社 撥水撥油剤
US5852148A (en) * 1991-07-10 1998-12-22 Minnesota Mining & Manufacturing Company Perfluoroalkyl halides and derivatives
US5350795A (en) * 1991-07-10 1994-09-27 Minnesota Mining And Manufacturing Company Aqueous oil and water repellent compositions which cure at ambient temperature
FR2683535B1 (fr) * 1991-11-12 1994-10-28 Atochem Nouveaux copolymeres fluores et leur utilisation pour le revetement et l'impregnation de substrats divers.
JPH0617034A (ja) * 1992-07-03 1994-01-25 Asahi Glass Co Ltd 撥水撥油剤組成物およびその製造方法
JP3275402B2 (ja) * 1992-12-02 2002-04-15 ダイキン工業株式会社 水性分散組成物およびその製法、ならびに撥水撥油剤および離型剤
JPH06228534A (ja) * 1993-02-01 1994-08-16 Daikin Ind Ltd 撥水撥油剤および防汚加工剤
JPH07173772A (ja) * 1993-12-21 1995-07-11 Asahi Glass Co Ltd 水分散型フッ素系撥水撥油剤およびその製造方法
US5466770A (en) * 1994-05-26 1995-11-14 Minnesota Mining And Manufacturing Company Fluorine-efficient oil- and water-repellent compositions
JP3298321B2 (ja) * 1994-08-31 2002-07-02 ダイキン工業株式会社 ビニリデンフルオライド系共重合体水性分散液、ビニリデンフルオライド系シード重合体水性分散液およびそれらの製法
JP3399107B2 (ja) * 1994-09-05 2003-04-21 ダイキン工業株式会社 撥水撥油性を有する防汚加工剤組成物
US5725789A (en) * 1995-03-31 1998-03-10 Minnesota Mining And Manufacturing Company Aqueous oil and water repellent compositions
AU6491096A (en) * 1995-07-13 1997-02-10 E.I. Du Pont De Nemours And Company Tetrafluoroethylene copolymer coating composition
JP3624615B2 (ja) * 1997-02-28 2005-03-02 ユニマテック株式会社 新規共重合体およびそれを含有する撥水撥油剤

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 198336 Derwent Publications Ltd., London, GB; Class A87, AN 1983-755313 XP002127327 & JP 58 126372 A (DAIICHI KOGYO SEIYAKU CO LTD), 27 July 1983 (1983-07-27) *
DATABASE WPI Section Ch, Week 198701 Derwent Publications Ltd., London, GB; Class A14, AN 1987-003812 XP002127326 & JP 61 264081 A (DAIKIN KOGYO KK), 21 November 1986 (1986-11-21) *
DATABASE WPI Section Ch, Week 199150 Derwent Publications Ltd., London, GB; Class A87, AN 1991-364597 XP002127328 & JP 03 243685 A (ASAHI GLASS CO LTD), 30 October 1991 (1991-10-30) *
DATABASE WPI Section Ch, Week 199408 Derwent Publications Ltd., London, GB; Class A14, AN 1994-062223 XP002127325 & JP 06 017034 A (ASAHI GLASS CO LTD), 25 January 1994 (1994-01-25) *
See also references of WO9748780A1 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7015275B1 (en) 1999-04-07 2006-03-21 Daikin Industries, Ltd. Aqueous water-and oil-repellent dispersion
WO2001032800A1 (fr) * 1999-10-29 2001-05-10 Asahi Glass Company, Limited Dispersion aqueuse pour repulsif eau et huile et procede de production
US6624268B1 (en) * 1999-10-29 2003-09-23 Asahi Glass Company, Limited Aqueous dispersion for water-and-oil repellant and process for producing the same
WO2002006433A1 (fr) * 2000-07-17 2002-01-24 Unilever Plc Composition de lessive comprenant un polymere antisalissure a base de perfluoroalkyle
EP1338637A1 (fr) * 2000-09-21 2003-08-27 Daikin Industries, Ltd. Dispersion aqueuse d'eau et de d'oleofuge de son procede de fabrication
EP1338637A4 (fr) * 2000-09-21 2008-03-05 Daikin Ind Ltd Dispersion aqueuse d'eau et de d'oleofuge de son procede de fabrication
WO2004033579A1 (fr) * 2002-10-10 2004-04-22 Seimi Chemical Co., Ltd. Composition de barriere anti-huile
EP1533356A1 (fr) * 2003-11-24 2005-05-25 3M Innovative Properties Company Composition fluorochimique pour rendre des substrats oléophobes et/ou hydrophobes
WO2005056711A1 (fr) * 2003-11-24 2005-06-23 3M Innovative Properties Company Composition chimique fluoree destinee a rendre des substrats oleofuges et/ou hydrofuges
CN102352000A (zh) * 2011-07-14 2012-02-15 浙江大学 有机-无机复合疏水/疏油表面处理剂的合成方法

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US6126849A (en) 2000-10-03
WO1997048780A1 (fr) 1997-12-24
KR20000016701A (ko) 2000-03-25
JPH108041A (ja) 1998-01-13
TW474985B (en) 2002-02-01
EP0909802A4 (fr) 2000-03-08

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